Catalyst for making acrylic acid from acrolein or propylene

ABSTRACT

A method for preparing acrylic acid by oxidation of acrolein over a new and improved catalyst providing conversions of acrolein of greater than 99% with yields of acrylic acid in excess of 95%. The catalyst consists essentially of the oxides of molybdenum, vanadium, chromium, copper and titanium and optionally silicon on an inert carrier. Catalysts useful in the process contain the elements previously mentioned in the atomic ratios of 
     
         Mo.sub.15 V.sub.5-10 Cu.sub.2-5 Cr.sub.0.2-2 Ti.sub.1-3.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of our copending applicationSer. No. 773,992. filed Mar. 3, 1977, now abandoned which is in turn acontinuation-in-part of application Ser. No. 678,274, filed Apr. 19,1976, now U.S. Pat. No. 4,049,577.

BACKGROUND OF THE INVENTION

In the process of making acrylic acid the most widely used processes arethose which oxidize propylene or acrolein to acrylic acid. Manydifferent combinations of metal oxides have been used as catalysts. Mostof these contain molybdenum oxide as the principal component. Some ofthe catalysts are effective in oxidizing the propylene directly toacrylic acid although this is frequently a function of the conditionsunder which the catalyst is used; others oxidize acrolein to the acid.In either case, any acrolein not converted, or acrolein made in theprocess of oxidizing propylene to acrylic acid, may be recycled to thefeed stream and subsequently oxidized to form the acrylic acid.

In addition to molybdenum oxide, the catalysts of the prior art containmany other metals (usually as their oxides) which promote the catalyticeffect of the molybdenum. The transition metals of Group VIII of theperiodic chart, including iron, cobalt and nickel, have been employed inmany such catalysts. Others selected from various groups of metals ofthe periodic chart have been employed. Thus, for example, titanium,vanadium, chromium, tungsten and manganese in groups IVB, VB, VIB andVIIB are known to be useful. From group IIA such metals as magnesium,calcium, strontium and barium; from groups IB and IIB copper, silver,zinc and cadmium; also from groups IA and VI sodium, potassium, antimonyand bismuth; all have been taught as catalytic promotor components.Phosphorous has been employed usually added as phosphoric acid or asmetal phosphates, as an essential part of many of the prior artcatalysts. Some of the early catalysts employed molybdenum oxide incombination with 1 or 2 other metals, e.g., U.S. Pat. No. 2,881,212which employed several metals as phosphomolybdates. In more recentyears, catalysts containing 3-6 or as many as 8-10 different metals havebeen disclosed.

The art known to the inventors as being closest to that of the presentinvention is found in U.S. Pat. Nos. 3,775,474; 3,833,649; 3,886,092which teach the use of Mo, V, Cr, Cu, and W in various combinations.None of these teach the use of tantalum, titanium, or niobium as taughtby the present invention, nor does the instant catalyst compositioncontain the tungsten taught by theabove three U.S. patents. Another U.S.Pat. No. 3,865,873, employs tantalum together with molybdenum andphosphorous, but contains none of the other components of the catalystof this invention. Inventors are also aware of British Pat. No.1,488,889 which employs oxides of Mo, V, Ti and a fourth componentselected from among Cu, Co, Cr, and/or Mn, as catalyst for oxidizing anunsaturated olefin to the corresponding acid.

The efficiency of the catalysts made from any particular combination ofmetals apparently is affected by the manner in which they are made, andwhether or not it is supported or in pelleted form. The porosity and thesurface area of either the pellet or the support are important to theperformance of the catalyst and will determine to some extent the amountof catalytic material employed on the support. It is extremely importantin the preparation of the catalyst to obtain uniform distribution of thevarious oxides contained therein, otherwise the effect of thecombination may be lost. The molybdenum and the various promotor metalsare added as their soluble salts, usually in acid solution. They aresometimes mixed together in the same solution, but because of possibleproblems with premature precipitation which would cause non-uniformityin the finished catalyst the metals are most frequently made up inseparate solutions which are in turn added together under the propercontrolled conditions. Generally, the final pH of the solutions isslightly on the acid side, at about pH 6-6.5. The solvent is thenevaporated from the solution of the catalyst components in the presenceof a support in order to burden it, when a support is used. If notsupported, the components are dried and pelleted. Most of the techniquesassociated with the manufacture of the catalyst are well known to theprior art. The particular techniques used to make the catalyst of thepresent invention will be enumerated and exemplified herein.

The parameters of feed composition, flow rate, temperature and pressureare well known to the prior art. Thus the aldehyde is usually present inthe feed stream from about 1-10 volume %, the remainder being molecularoxygen (0.8 to 21 vol. %) and inert gas. Steam is frequently used as theinert gas although since air is usually employed as the source ofoxygen, nitrogen is most often present as an inert gas component.Temperatures employed are within the range of 200°-400° C. and apressure of from about 1-10 atm. is commonly used. Contact times areusually on the order of 0.4 to about 15 seconds depending upon thetemperature employed and the efficiency of the particular catalyst.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is the vapor phase oxidation of acrolein toacrylic acid over a catalyst consisting essentially of molybdenum,vanadium, chromium, copper and at least one of tantalum, titanium andniobium. Silicon may also be employed. All of these elements are presentin the form of their oxides and the catalyst is preferably employed onan inert support. The operable ratio of the atoms of the above elementsin the catalyst of this invention is

    Mo.sub.15 V.sub.5-10 Cu.sub.2-5 Cr.sub.0.2-2 M.sub.0.1-3 Si.sub.1-5

where M is tantalum, titanium, niobium or mixtures thereof. A preferredcatalyst is one containing the above atomic ratios but wherein M is Tiand is employed at a ratio of about 1-3. A more preferred catalyst isone having a composition of

    Mo.sub.15 V.sub.5-7 Cu.sub.2.4-2.8 Cr.sub.0.7-0.8 Ti.sub.1.5-2 Si.sub.1-5,

it being understood that silicon is optional in both operable andpreferred catalysts.

The tantalum pentoxide which is employed as a component is insoluble anddifficult to incorporate into the catalyst mixture and as a result isgenerally slurried in a solution of the other components. A particularlypreferred method of making a solution of catalyst components is toemploy the tantalum pentoxide as a colloidal suspension. Thecommercially available oxide powder is first run through a colloid millprior to mixing with the silica (when silica is employed) and then addedto the remaining components as described in Examples 1 and 16. The useof the finely divided colloid produces a superior catalyst.

As previously mentioned, it is known in the art that the amount ofcatalyst used will depend, at least in part, upon the porosity andsurface area of the particular inert support employed. In the presentinvention the total amount of catalytic oxides burdened on the supportis from about 13% to about 30% by weight based on the combined weight ofcatalyst and support. A preferred burden is from about 18% to about 23%.The preferred support is alumina and the surface area of the preferredsupport should be not more than 2 m² /g with a porosity of 35-65%, 90%of the pores being in the diameter range of 50-1500 microns.

EXAMPLE 1 Preparation of Catalyst

In a representative preparation of the catalyst of the presentinvention, the first solution was prepared by heating 1400 mls ofdistilled water to which was added 172.7 gms of ammonium molybdate, 43.9gms of ammonium meta-vanadate, and 6.0 gms of ammonium dichromate. Asecond solution was prepared by adding 43.9 gms of cupric nitrate to 75mls of distilled water which had been acidified with 3 mls ofconcentrated nitric acid. A third solution was prepared by adding 27.5gms of tantalum pentoxide to 28.3 mls of Ludox L.S. (a 30% colloidalsolution of silica).

The second solution was added drop-wise to the first solution withstirring and heating. Upon completion of this addition, the thirdsolution was added to the other two with continued heat and stirring.The carrier support (Norton S.A. 5205, 1/4-inch spheres of alumina) waspreheated in an oven at 150° C. and then added to the composite solutionabove with continued heating and stirring to remove the excess water.When most of the water had been removed, the carrier was placed in anoven at 150° C. for 1 hour to dry it. The dried catalyst was thencalcined for a period of about 6.5 hours the temperature being graduallyincreased from about 200° to 400° C. over a period of about 1.5 hours.The temperature was then maintained at 400° C. for the remainder of thetime. The finished catalyst was removed and cooled prior to use. Thecatalyst prepared as above contained about 19.2 wt. % of the metaloxides on the catalyst support, and the atomic ratios of the metals were

    Mo.sub.15 V.sub.5.7 Cr.sub.0.73 Cu.sub.2.76 Ta.sub.1.89 Si.sub.2.59.

EXAMPLE 1-A

In the manner of Example 1, another catalyst was prepared in whichtitanium was substituted for tantalum. After the first two solutions hadbeen combined as in Example 1, 7.3 g of titanium dioxide was added tothe combination solution while heating and stirring was continued. Theremaining steps of making the catalyst were carried out as above. Thecatalyst contained 19.2 wt. % of the metal oxides on the support and hadthe following atomic ratio of metals:

    Mo.sub.15 V.sub.5.76 Cr.sub.0.72 Cu.sub.2.79 Ti.sub.1.39.

EXAMPLE 2 Utilization of Catalyst

The catalyst of Example 1 was placed in a stainless steel reactor madeof a 1-inch tube 10 feet long within a concentric pipe which contained aheat exchange fluid for temperature control. The feed to the reactorcontained 5.6 mole % acrolein, 30 mole % nitrogen (as diluent) andoxygen; the oxygen to acrolein mole ratio being 1.48. Temperature in thereactor was 300° C. Contact time was 2.9 seconds. This feed stream whenpassed through the reactor over the above catalyst resulted in aconversion of 99% of the acrolein and gave a selectivity to acrylic acidof 93.4% with 4.4% going to carbon oxides. In like manner, catalysts ofvarying compositions were tested. The mole % acrolein in the feed ofeach of the following Examples was in the range of from about 4.5 toabout 5.5%. The results are shown in Table I.

                                      TABLE I                                     __________________________________________________________________________                                           Selectivity                            Example                                                                            Catalyst Components  Temp.                                                                             Time                                                                             Conv.     % Carbon                           Number                                                                             Mo V  Cr Cu Ta Nb Si (°C.)                                                                      (sec)                                                                            (% Acrn.)                                                                           % A A                                                                             Oxides                             __________________________________________________________________________     3   15 5.7                                                                              0.72                                                                             2.76                                                                             3.08                                                                             -- 2.59                                                                             300 2.7                                                                              91    92  7.0                                 4   15 6.67                                                                             0.93                                                                             3.22                                                                             2.2                                                                              -- 2.92                                                                             280 3.5                                                                              95    89  9.6                                 5   15 5.7                                                                              0.72                                                                             2.76                                                                             1.89                                                                             -- -- 289 2.5                                                                              95.1  94.8                                                                              5.2                                 6   15 5.7                                                                              0.72                                                                             2.76                                                                             1.89                                                                             -- 2.59                                                                             300 2.9                                                                              99.5  93.0                                                                              6.0                                 7   15 5.7                                                                              1.09                                                                             2.76                                                                             1.89                                                                             -- -- 301 2.2                                                                              89.8  91.2                                                                              8.8                                 8   15 5.71                                                                             0.74                                                                             2.76                                                                             -- 1.78                                                                             4.2                                                                              283 3.7                                                                              96.0  88  9.5                                 9*  15 5.47                                                                             0.71                                                                             2.64                                                                             1.82                                                                             -- 2.9                                                                              276 3.2                                                                              98    91  9.0                                10   15 7.48                                                                             1.51                                                                             2.75                                                                             -- 1.14                                                                             -- 280 3.1                                                                              89.4  88.1                                                                              10.2                               11** 15 5.75                                                                             0.73                                                                             2.78                                                                             1.89                                                                             -- -- 289 2.2                                                                              94.9  96.3                                                                              3.7                                __________________________________________________________________________      *Only 2.6 mole % acrolein was employed in the feed stream                    **Catalyst was made employing a colloidal form of tantalum               

EXAMPLE 2-A

In the manner of Example 1A other catalysts were prepared containingvarious amounts of titanium. These were tested as in Example 2 and theresults given in Table II. All components are the same as in Example 1Aexcept titanium, the atomic ratio of which is given in the columnlabeled (x).

                  TABLE II                                                        ______________________________________                                        (Mo.sub.15 V.sub.5.76 Cr.sub.0.72 Cu.sub.2.79 Ti.sub.(x))                     Cat-        Temp    Time Conv.  Selectivity                                   alyst                                                                              (x)    (°C.)                                                                          (sec)                                                                              % Acrn.                                                                              % A A % Carbon Oxides                         ______________________________________                                        A    0.99   291     3.43 87.7   94.0  5.9                                     B.sub.1                                                                            1.19   291     3.45 94.6   93.8  6.2                                     B.sub.2 *                                                                          1.19   305     3.39 95.7   91.4  8.6                                     C    1.39   290     3.57 99.2   95.2  5.4                                     D.sub.1                                                                            1.46   280     3.95 98.5   95.0  5.0                                     D.sub.2 *                                                                          1.46   304     3.40 96.7   90.0  8.3                                     E    1.85   291     2.62 98.7   94.2  5.8                                     F    2.18   294     3.51 97.3   93.8  6.2                                     G    3.0    291     3.3  98.4   92.2  6.9                                     ______________________________________                                         *The feed compositions of these examples contained about 39.3 mole %          nitrogen as diluent compared to 30 mole % for the remaining examples.    

That titanium oxide in the compositions of the invention is equivalentto or better than the oxides of tantalum or niobium can be seen bycomparing the examples in Tables I and II. Of particular interest areExamples 3, 5 and 8 in Table I and G and E in Table II.

COMPARATIVE EXAMPLES

In order to show that each of vanadium, chromium, copper and tantalum orniobium is necessary to assure the good performance of the catalyst ofthe present invention, catalyst compositions substantially identical tothat of Example 5, save one of the above components, were run in themanner of Example 2. Results are shown in Table III wherein catalystsoutside the scope of the present invention were employed.

                                      TABLE III                                   __________________________________________________________________________                                           Selectivity                            Example                                                                            Catalyst Components  Temp.                                                                             Time                                                                             Conv.     % Carbon                           Number                                                                             Mo V  Cr Cu Ta Nb Si (°C.)                                                                      (sec)                                                                            (% Acrn.)                                                                           % A A                                                                             Oxides                             __________________________________________________________________________    12   15 -- 0.7                                                                              2.78                                                                             1.9                                                                              -- 2.63                                                                             310 2.7                                                                               4.3  37  63                                 13   15 5.76                                                                             -- 2.78                                                                             1.9                                                                              -- 2.59                                                                             310 2.7                                                                              66.8  86.4                                                                              14.5                               14   15 5.75                                                                             0.7                                                                              -- 1.9                                                                              -- 2.63                                                                             310 2.7                                                                              31.4  66.7                                                                              33.3                               15   15 5.75                                                                             0.7                                                                              2.78                                                                             -- -- -- 301 2.7                                                                              92.8  83.2                                                                              17.2                               __________________________________________________________________________

As can be seen from Table III, omitting any one of vanadium, chromium,copper and tantalum will give both lowered conversions and selectivitiesas well as high carbon losses.

EXAMPLE 16

In a preferred preparation of the catalyst of the present invention, afirst solution was prepared by heating 6000 ml of distilled water towhich was added 1427.6 g of ammonium molybdate, 362.8 g of ammoniummetavanadate, and 49.0 g of ammonium dichromate. A second solution wasprepared by adding 363 g of cupric nitrate to 150 ml of distilled waterwhich had been acidified with 20 ml of concentrated nitric acid. A thirdsolution was prepared by adding 226.4 g colloidal tantalum pentoxides,less than 1 micron in size, to 500 ml water.

The second solution was added drop-wise to the first solution withstirring and heating. Upon the completion of this addition, the thirdsolution was added to the other two with continued heat and stirring.The carrier support (Norton S.A. 5205, 1/4-inch spheres of alumina) waspreheated in an oven at 150° C. and then added to the composite solutionabove with continued heating and stirring to remove the excess water.When most of the water had been removed, the carrier was placed in anoven at 150° C. for 1 hour to dry it. The dried catalyst was thencalcined for a period of about 6.5 hours the temperature being graduallyincreased from about 200° to 400° C. over a period of about 1.5 hours.The temperature was then maintained at 400° C. for the remainder of thetime. The finished catalyst was removed and cooled prior to use. Thecatalyst prepared as above contained about 22.3 wt. % of the metaloxides on the catalyst support, and the atomic ratios of the metals were

    Mo.sub.15 V.sub.5.75 Cr.sub.0.73 Cu.sub.2.78 Ta.sub.1.9.

The above catalyst, when employed to oxidize acrolein in the manner ofExample 2, gave a 99.8% conversion of acrolein and a selectivity of96.5% to acrylic acid.

EXAMPLE 17

A catalyst for the oxidation of propylene to acrolein disclosed by thepresent inventors in an application filed in the U.S. Patent andTrademark Office, Dec. 15, 1975, (Ser. No. 640,616 now U.S. Pat No.4,049,577) was employed in conjunction with a catalyst of the presentinvention in sequential operation in the following manner:

A metal oxide composition containing atomic metal ratios of Mo₁₅ Co₆.7Fe₁.35 Bi₁.3 K₀.011 formed into pellets 1/4-inch diameter and 1/4-inchthick was placed into a first column, stainless steel tubular reactor 12ft. tall and 1.25-inch diameter. A conduit connected this first columnwith a second column 19 ft. long × 1.5-inch I.D. of the same stainlesssteel into which was packed the supported catalyst of Example 16. Eachcolumn was heated by means of a heat exchange fluid flowing through anouter concentric tube. To the first column was fed a gas streamcontaining 5.3 mole percent propylene, 9.4 mole percent oxygen, andbalance nitrogen at a pressure of 28.7 psig and a flow rate of 12.5lb/hr to obtain a contact time of 2.19 seconds. The feed was preheatedto a temperature of 325° C. and the first reaction columnm wasmaintained at 331° C. The exit stream was passed through the conduit tothe second column which was maintained at 279° C. Contact time in thesecond column was 4.87 seconds. The exit gases from the second columnwere quenched and the non-condensible gases were recycled to the firstcolumn. Conversion of propylene was 98.3% and yield to acrylic acid was89%.

Each of the catalysts employed in the preceding 17 examples was adheredto a spherical alumina support of about 1/4-inch diameter. In Table IVthe support employed for each catalyst and the loading (weight %catalyst employed based on total weight of catalyst and support) isgiven. Supports A, B and C had different porosities and surface areas asfollows:

A=49-55% porosity; 90% of the pores in 50-1500 microns range; 0.005-0.5m² /g surface area.

B=60.2% porposity; 90% of the pores in 50-1500 microns range; 0.024 m²/g surface area.

C=38-42% porosity; 90% of the pores in 50-1500 microns range; 0.005-0.04m² /g surface area.

                  TABLE IV                                                        ______________________________________                                        Example                   Loading                                             Number       Carrier      (wt. %)                                             ______________________________________                                        1            A            19.2                                                2            A            19.2                                                3            B            19.8                                                4            C            18.6                                                5            A            21.6                                                6            A            24.0                                                7            A            24.6                                                8            C            13.1                                                9            C            21.7                                                10           A            26.4                                                11           A            24.3                                                12           A            23.7                                                13           A            24.0                                                14           A            24.3                                                15           A            23.9                                                16           A            22.3                                                17           A            22.3                                                ______________________________________                                    

We claim:
 1. A supported catalyst suitable for oxidizing acrolein toacrylic acid which contains oxides of molybdenum, vanadium, chromium,copper and titanium on an inert support, wherein the atomic ratios ofthe metals are

    Mo.sub.15 V.sub.5-10 Cr.sub.0.2-2 Cu.sub.2-5 Ti.sub.1-3.


2. The catalyst of claim 1 which additionally contains silicon as itsoxide in the ratio of 1-5 atoms of silicon.
 3. A supported catalystsuitable for oxidizing acrolein to acrylic acid which contains oxides ofmolybdenum, vanadium, chromium, copper and titanium on an inert support,wherein the atomic ratios of the metals are

    Mo.sub.15 V.sub.5-7 Cr.sub.0.7-0.8 Cu.sub.2.4-2.8 Ti.sub.1.5-2.


4. A supported catalyst suitable for oxidizing acrolein to acrylic acidwhich contains oxides of molybdenum, vanadium, chromium, copper andtitanium on an inert support, wherein the atomic ratios of the metalsare

    Mo.sub.15 V.sub.5-7 Cr.sub.0.7-0.8 Cu.sub.2.4-2.8 Ti.sub.1.5-2.

and which additionally contains silicon as its oxide in the ratio of 2-3atoms of silicon.
 5. A supported catalyst suitable for oxidizingacrolein to acrylic acid which contains oxides of molybdenum, vanadium,chromium, copper and titanium on an inert support, wherein the atomicratios of the metals are

    Mo.sub.15 V.sub.5-7 Cr.sub.0.7-0.8 Cu.sub.2.4-2.8 Ti.sub.1.5-2.

and wherein the support is alumina having a surface area of not morethan 2 m² /g and a porosity of 35-65%, 90% of the pores being in therange of 50-1500 microns in diameter.